WO2010109863A1 - Système de pile à combustible - Google Patents

Système de pile à combustible Download PDF

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Publication number
WO2010109863A1
WO2010109863A1 PCT/JP2010/002092 JP2010002092W WO2010109863A1 WO 2010109863 A1 WO2010109863 A1 WO 2010109863A1 JP 2010002092 W JP2010002092 W JP 2010002092W WO 2010109863 A1 WO2010109863 A1 WO 2010109863A1
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Prior art keywords
fuel cell
catalyst
cell system
temperature
raw material
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PCT/JP2010/002092
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English (en)
Japanese (ja)
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龍井洋
田口清
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パナソニック株式会社
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Application filed by パナソニック株式会社 filed Critical パナソニック株式会社
Priority to JP2011505872A priority Critical patent/JP5173019B2/ja
Priority to US13/057,657 priority patent/US8507136B2/en
Priority to CN2010800024699A priority patent/CN102138240A/zh
Priority to EP10755665A priority patent/EP2413411A4/fr
Publication of WO2010109863A1 publication Critical patent/WO2010109863A1/fr

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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • H01M8/04373—Temperature; Ambient temperature of auxiliary devices, e.g. reformers, compressors, burners
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    • H01M8/04432—Pressure differences, e.g. between anode and cathode
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    • C01B2203/08—Methods of heating or cooling
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Definitions

  • the present invention relates to a fuel cell system that generates electric power by supplying a reformed gas generated by reforming a hydrocarbon-based material to a fuel cell.
  • the fuel cell supplies hydrogen or a hydrogen rich gas to one of the electrodes sandwiching the electrolyte, and supplies an oxidant gas such as air containing oxygen to the other to generate electricity by an electrochemical reaction.
  • an oxidant gas such as air containing oxygen
  • city gas and hydrocarbon source gas such as LPG are filled with a reforming catalyst at about 700 ° C.
  • a reforming catalyst at about 700 ° C.
  • carbon monoxide which is contained in an amount of about 10 to 15% in the reformed gas coming out of the reforming section is produced as a by-product. Since carbon monoxide poisons the electrode catalyst of the fuel cell to reduce the power generation capacity, it is necessary to remove the carbon monoxide concentration in the reformed gas to 100 ppm or less, preferably 10 ppm or less.
  • a shift catalyst is caused to react the carbon monoxide and steam in the reformed gas coming out of the reforming unit to cause water gas shift reaction with hydrogen and carbon dioxide
  • the reformed portion filled with the reformed portion, and the reformed gas whose concentration of carbon monoxide is reduced in the transformed portion and air are supplied to cause selective oxidation reaction between carbon monoxide and oxygen in the air, and the concentration of carbon monoxide in the reformed gas Is connected to a selective oxidation unit filled with a selective oxidation catalyst that reduces the concentration of hydrogen to 10 ppm or less.
  • the water gas shift reaction is performed at about 200 ° C. or more in the metamorphic part
  • the selective oxidation reaction is performed at about 100 ° C. in the selective oxidation part.
  • a burner unit for temperature rise is provided in the reforming unit.
  • the burner unit is configured to use hydrogen in the reformed gas (hereinafter sometimes referred to as "off gas") not used for power generation of the fuel cell together with air supplied to the burner unit during power generation of the fuel cell system.
  • the temperature of the reforming catalyst at which the reforming reaction, which is an endothermic reaction, is carried out by combustion is maintained at about 700.degree. Further, at the time of start-up operation of the fuel cell system, the burner unit burns the raw material gas before hydrogen generation and the mixed gas of the raw material gas and hydrogen to raise the temperature of the reforming catalyst.
  • a hydrogen production apparatus in which a reforming unit provided with a burner unit, a transformation unit, and a selective oxidation unit are connected may be described as a fuel processor as appropriate.
  • the fuel processor when stopping power generation of the fuel cell system, the fuel processor performs purge of reformed gas containing water vapor in the fuel processor and pressure in the fuel processor at positive pressure.
  • Supply source gases such as city gas and LPG.
  • the raw material gas is supplied to the burner unit via the fuel processor and burned together with air. Raise the temperature.
  • the components of the raw material gas adsorbed to each catalyst are desorbed and supplied to the burner unit together with the raw material gas supplied to the fuel processor. Therefore, the amount of the raw material gas actually supplied to the burner unit is larger than the raw material gas supplied to the fuel processor by only the component of the raw material gas which has been desorbed. Then, the ratio of the raw material gas to the air deviates, and incomplete combustion occurs in the burner section.
  • the present invention is intended to solve the above-mentioned conventional problems, and it is an object of the present invention to provide a fuel cell system capable of stable start-up operation along with stable combustion of a burner unit at start-up operation of a fuel cell system.
  • a fuel cell system includes a reforming unit that reforms a mixed gas of a source gas and steam with a reforming catalyst to generate a reformed gas containing hydrogen;
  • the reformed gas produced in the reforming section is brought into contact with a carbon monoxide reduction catalyst to reduce carbon monoxide in the reformed gas, and the reformed gas passing through the carbon monoxide reduction section
  • a fuel cell system comprising a raw material gas supply device for supplying a raw material gas to a reforming portion, a reforming portion or directly to a burner portion, wherein the burner portion burns when the fuel cell system starts up.
  • the blower Supplied by the source gas supply system Depending on the amount of gas and at least one of the components of the raw material gas adsorbed to one of the reforming catalyst and the carbon monoxide reduction catalyst, the blower sends to the burner unit with the blower according to the amount of desorbed starting material gas It adjusts the amount of air.
  • a fuel cell system capable of performing stable start-up operation by heating each catalyst in the fuel processor to a predetermined temperature by burning the raw material gas in the burner portion it can.
  • a schematic view showing a configuration of a fuel cell system according to Embodiment 1 of the present invention Principal part sectional view explaining a fuel processor used for a fuel cell system in the embodiment A schematic diagram showing the relationship between the temperature of the shift catalyst in the shift section of the fuel cell system of the embodiment and the amount of desorbed source gas released from the shift catalyst Flow chart showing the flow of control of the main part during start-up operation of the fuel cell system of the embodiment Characteristic diagram showing the state of temperature rise of the reforming catalyst, the shift catalyst, and the selective oxidation catalyst at the time of start-up operation in the fuel cell system of the embodiment Flow chart for explaining the control flow of the main part of another method of start-up operation in the fuel cell system of the embodiment
  • the schematic diagram which shows the structure of the fuel cell system in Embodiment 2 of this invention Flow chart showing the flow of control of the main part during start-up operation of the fuel cell system of the embodiment Flow chart for explaining the control flow of the main part of another method of start-up operation in the fuel cell system of the embodiment
  • a reforming unit that reforms a mixed gas of a source gas and steam with a reforming catalyst to generate a reformed gas containing hydrogen, and a reformed gas generated by the reforming unit.
  • a carbon monoxide reduction unit for reducing carbon monoxide in the reformed gas by contacting with a carbon monoxide reduction catalyst, a fuel cell for generating electric power with hydrogen in the reformed gas passing through the carbon monoxide reduction unit, a fuel cell A burner unit that burns the off gas containing at least one of the hydrogen and the at least one of the source gas and the reformed gas using combustion air supplied by a blower, the source gas is reformed, and the reformer A fuel cell system comprising: a raw material gas supply device for supplying to a burner unit directly or via a raw material gas, the raw material gas supplied from the raw material gas supply device to be burned in the burner unit at start-up operation of the fuel cell system; Reforming catalyst and carbon monoxide reduction catalyst On the other hand, depending on the amount of the desorbed come desorbed material gas of the components of the adsorbed have raw material gas to a fuel cell system for adjusting the amount of combustion air to be sent to the burner portion in the blower.
  • the ratio of the amount of combustion air supplied to the burner portion to the total amount of the amount of source gas supplied from the source gas supply device and the amount of desorbed source gas supplied from desorption is set to a predetermined ratio. Can be adjusted to achieve stable combustion. As a result, it is possible to realize a fuel cell system that performs stable start-up operation by raising each catalyst in the fuel processor to a predetermined temperature.
  • the fuel cell system is provided with a heating means for heating at least one of the reforming catalyst and the carbon monoxide reduction catalyst at start-up operation of the fuel cell system.
  • At least the desorption raw material of the raw material gas and the desorption raw material gas supplied by the raw material gas supply device supplied to the burner unit during start-up operation of the fuel cell system It further comprises measuring means for measuring the flow rate of the gas.
  • a fourth invention is the flow meter according to the third invention, wherein the measuring means measures at least the flow rate of the desorbed source gas.
  • the flow rate of the raw material gas supplied to the burner unit can be measured relatively easily relatively. Therefore, the flow rate of the combustion air supplied to the burner unit is the flow rate of the raw material gas supplied to the burner unit It is possible to adjust accordingly and to perform stable combustion in the burner section.
  • the measuring means is a pressure gauge for detecting at least the pressure of the desorbed source gas.
  • the raw material gas supplied to the burner portion is the flow rate of combustion air supplied to the burner portion It is possible to adjust in accordance with the flow rate of H. It is possible to perform stable combustion in the burner section.
  • a sixth aspect of the invention is the exhaust gas analysis means for detecting the concentration of at least one component of the combustion exhaust gas components after burning in the burner portion in the first or second invention, wherein the detection is performed by this exhaust gas analysis means The amount of combustion air is adjusted based on the concentration.
  • a seventh invention according to the first or second invention includes one or more temperature sensors for detecting the temperature of at least one of the reforming catalyst and the carbon monoxide reduction catalyst, and the reforming catalyst detected by the temperature sensor Of the raw material gas adsorbed in at least one of the reforming catalyst and the carbon monoxide reduction catalyst which are burned in the burner unit during start-up operation of the fuel cell system based on the temperature of at least one of the catalyst and the carbon monoxide reduction catalyst Estimate the amount of desorbed desorbed source gas inside.
  • the amount of the desorbed raw material gas desorbed relatively accurately can be estimated with a simple configuration, and the combustion in the burner section can be stabilized.
  • An eighth invention according to the first, second or seventh invention further comprises timer means for measuring an elapsed time from the heating start of the heating means, and based on the time measured by the timer means, the burner unit Among the components of the source gas adsorbed on at least one of the reforming catalyst to be burned and the carbon monoxide reduction catalyst, the amount of the desorbed source gas is estimated.
  • the amount of desorbed source gas can be detected with a simple configuration.
  • heating of at least one of the reforming catalyst and the carbon monoxide reduction catalyst is started by the heating means when the fuel cell system is started, and the heating is performed.
  • the source gas supply device is operated after a predetermined time has elapsed from the start of heating by the means.
  • a tenth invention provides the fuel cell according to any of the second, seventh or eighth inventions, including one or more temperature sensors for detecting the temperature of at least one of the reforming catalyst and the carbon monoxide reduction catalyst.
  • heating of at least one of the reforming catalyst and the carbon monoxide reduction catalyst is started by the heating means, and the source gas supply device is operated after the temperature detected by the temperature sensor becomes equal to or higher than a predetermined temperature.
  • the desorption takes place in a time zone assuming combustion by only the desorbed raw material gas desorbed in the burner section. Even if a misfire occurs because the amount of desorbed source gas that is released is smaller than expected, the misfire can be detected by the temperature rise rate of the catalyst by the temperature sensor.
  • An eleventh aspect of the present invention is the method according to any one of the second, seventh or eighth aspects, wherein the raw material gas supply device and the heating means are operated at startup of the fuel cell system and the burner portion supplies the raw material gas from the raw material gas supply device. After the raw material gas is burned for a predetermined time, the operation of the raw material gas supply device is stopped, and the raw material gas supply device is operated after a predetermined time has elapsed from the start of heating of the heating means.
  • the raw material gas supply device is operated at startup of the fuel cell system and the burner portion supplies the raw material gas from the raw material gas supply device.
  • a twelfth invention is the fuel cell according to any one of the second, seventh or eighth inventions, including one or more temperature sensors for detecting the temperature of at least one of the reforming catalyst and the carbon monoxide reduction catalyst.
  • the source gas supply device and the heating means are operated, and after a predetermined time has elapsed from the start of heating by the heating means or after the temperature sensor detects the first predetermined temperature or more, the operation of the source gas supply device is stopped. After the temperature sensor detects the second predetermined temperature or more, the source gas supply device is operated.
  • the heating means is an electric heater.
  • the start and end of heating of the catalyst can be controlled relatively easily.
  • the control of the heating amount is easy by the on / off control and the input voltage control, the electric heater can easily control the temperature rising rate of the catalyst.
  • the rate of temperature increase is reduced to suppress the deterioration of the catalyst due to a rapid temperature change, or the rate of temperature increase is increased to shorten the start-up time, thereby eliminating the amount of desorbed source gas desorbed from the catalyst. It becomes possible to adjust.
  • the heating means comprises a heating burner portion, and at least one of the reforming portion and the carbon monoxide reducing portion is a combustion exhaust gas of the heating burner portion. Heat up. Thereby, the exhaust heat from the combustion of the heating burner portion can be effectively used for heating the catalyst. Therefore, it is possible to realize a fuel cell system provided with start-up characteristics excellent in energy efficiency.
  • the burner portion is used as a heating burner portion.
  • the burner portion is used as a heating burner portion.
  • piping for supplying the raw material gas and the combustion air to the burner portion can be simplified.
  • the burner unit as the heating means can be realized with a simple configuration, it is possible to suppress the size and complexity of the fuel cell system.
  • FIG. 1 is a schematic view showing a configuration of a fuel cell system according to Embodiment 1 of the present invention.
  • the fuel cell system 1 of the present embodiment includes a fuel cell 2, a fuel processor 3, a water vapor generator 4, a controller 5, a raw material gas supply device 6, a combustion air fan 7 and a cathode air blower. And at least eight.
  • the combustion air fan 7 is a blower for supplying combustion air to a burner unit described later.
  • LPG is used as a source gas supplied to the fuel cell system 1, and a LPG cylinder (not shown) is connected to the source gas supply device 6 outside the fuel cell system 1.
  • other hydrocarbon-based raw materials such as city gas can also be used as the raw material gas.
  • the sulfur compound to be added as an odorant to the hydrocarbon-based raw material is added to the desulfurizing unit (shown in FIG. 1) on the upstream side of the raw material gas supply unit 6 or between the raw material gas supply unit 6 and the fuel processor 3. It is removed when passing through.
  • the fuel cell 2 has a structure in which the solid polymer electrolyte membrane 2a is sandwiched between the anode electrode 2b and the cathode electrode 2c. Then, a reformed gas containing a large amount of hydrogen generated by the fuel processor 3 is supplied to the anode electrode 2b, and air is supplied to the cathode electrode 2c by the cathode air blower 8 to generate power.
  • the fuel processor 3 has a configuration in which the reforming unit 9, the conversion unit 10 constituting the carbon monoxide reduction unit, and the selective oxidation unit 11 are sequentially connected.
  • the reforming catalyst 9 a is filled in the reforming unit 9, the shift catalyst 10 a is filled in the shift unit 10, and the selective oxidation catalyst 11 a is filled in the selective oxidation unit 11.
  • a burner unit 12 is provided in the reforming unit 9, and hydrogen in off gas including hydrogen which is not used at the time of power generation by the fuel cell 2 is supplied to the reforming air fan 7 via the combustion air path 7a. It burns with the air sent to the burner unit 12. Then, it is discharged to the outside of the fuel cell system 1 through the flue gas passage 13 as the flue gas.
  • the combustion exhaust gas passage 13 prevents the insides of the reforming unit 9, the shift unit 10 and the selective oxidation unit 11 from the burner unit 12 from being in direct contact with the reforming catalyst 9a, the shift catalyst 10a and the selective oxidation catalyst 11a. It is provided in the structure which passes through the divided space.
  • the source gas supplied from the source gas supply path 14 to the space filled with the reforming catalyst 9a of the reforming unit 9 by the source gas supply device 6 first passes through the packed bed of the reforming catalyst 9a.
  • the source gas is discharged from the reforming unit 9, supplied to the space filled with the shift catalyst 10a of the shift unit 10, and passes through the packed bed of the shift catalyst 10a.
  • the raw material gas is discharged from the shift conversion unit 10, supplied to the space filled with the selective oxidation catalyst 11a of the selective oxidation unit 11, and passes through the packed bed of the selective oxidation catalyst 11a.
  • the source gas is circulated through the source gas supply path 14 and the source gas path 15 so as to exit from the selective oxidation unit 11 to the source gas path 15.
  • the raw material gas passage 15 has a structure branched to the fuel cell inlet passage 15 a and the fuel cell bypass passage 15 b at the upstream side of the inlet of the fuel cell 2 on the side of the anode electrode 2 b.
  • the fuel cell inlet passage 15a is connected to the inlet side on the anode electrode 2b side of the fuel cell 2, and the off gas passage 15c is connected to the outlet side.
  • the side of the off gas path 15 c not connected to the fuel cell 2 is connected to the fuel cell bypass path 15 b of the source gas path 15.
  • a fuel cell bypass valve 16 is installed in the fuel cell bypass path 15b
  • a fuel cell inlet valve 17 is installed in the fuel cell inlet path 15a
  • a fuel cell outlet valve 18 is installed in the off gas path 15c.
  • the control unit 5 controls the opening and closing of the fuel cell bypass valve 16, the fuel cell inlet valve 17 and the fuel cell outlet valve 18 to switch the source gas passage 15 between the fuel cell inlet passage 15 a and the fuel cell bypass passage 15 b.
  • the source gas passage 15 is connected to the burner unit 12 at the downstream side where the fuel cell bypass passage 15b and the off gas passage 15c are connected.
  • a water vapor path 4 a for mixing the water vapor from the water vapor generator 4 into the source gas and supplying the mixed gas to the reforming unit 9 as necessary.
  • FIG. 2 is a main part cross-sectional view for explaining the fuel processor 3 used in the fuel cell system according to Embodiment 1 of the present invention.
  • the first cylindrical body 20, the second cylindrical body 21, the third cylindrical body 22 and the fourth cylindrical body 23 are arranged in a substantially concentric manner from the inner side and provided. ing. Then, the combustion exhaust gas path 13 is constituted by the space between the first cylindrical body 20 and the second cylindrical body 21, and the first gas flow path 24 is the space between the second cylindrical body 21 and the third cylindrical body 22. The second gas flow passage 25 is formed in a space between the third cylindrical body 22 and the fourth cylindrical body 23. Further, in the inner space of the first cylindrical body 20, a burner unit 12, a raw material gas passage 15 for supplying the raw material gas and the off gas to the burner unit 12, a combustion air passage 7a, and a combustion chamber 26 are provided. There is. The combustion chamber 26 and the combustion exhaust gas passage 13 communicate with each other via an exhaust gas return portion 27 in the vicinity of the end thereof. Similarly, the first gas flow passage 24 and the second gas flow passage 25 communicate with each other via the source gas turnaround portion 28 near the end thereof.
  • the first gas flow path 24 is provided with a reforming portion 9 in which, for example, a spherical reforming catalyst 9a in which metal ruthenium is supported on an alumina carrier is filled.
  • a nickel catalyst, a platinum catalyst, a platinum group catalyst such as rhodium, or the like can be used as the reforming catalyst 9a.
  • a cylindrical shape or the like it is also possible to use a cylindrical shape or the like as the shape of the reforming catalyst 9a.
  • the second gas flow path 25 includes, for example, a metamorphic portion 10 filled with a metamorphic catalyst 10a such as Cu—Zn (specifically, MDC-7 manufactured by Zude Chemie Co., Ltd.), and selection of spherical ruthenium based, for example.
  • a metamorphic catalyst 10a such as Cu—Zn (specifically, MDC-7 manufactured by Zude Chemie Co., Ltd.), and selection of spherical ruthenium based, for example.
  • a selective oxidation unit 11 filled with an oxidation catalyst 11a is provided.
  • platinum-based catalysts can also be used as the shift catalyst 10a and the selective oxidation catalyst 11a.
  • a selective oxidation air supply path 11 b for performing an oxidation reaction with the selective oxidation catalyst 11 a is connected to the selective oxidation unit 11.
  • a source gas supply path 14 is connected above the first gas flow path 24.
  • the selective oxidation unit 11 has been described as an example using the selective oxidation unit 11 that reduces the concentration of carbon monoxide by the selective oxidation reaction. However, for example, the concentration of carbon monoxide is reduced by the methanation reaction. It is also good.
  • the shift conversion unit 10 is provided with a shift temperature sensor 10b that measures the temperature of the shift catalyst 10a.
  • the shift temperature sensor 10b is a desorbed raw material from which the source gas adsorbed to the shift catalyst 10a is desorbed by the control unit 5 based on the detected temperature of the shift catalyst 10a. It can also be used to estimate the amount of gas.
  • the exterior of the fuel processor 3 is covered with a heat insulating material (not shown), and is provided in consideration of the heat insulation of each part so that a temperature balance to be described later is established.
  • FIG. 3 is a schematic view showing the relationship between the temperature of the shift catalyst 10a of the shift section 10 of the fuel cell system 1 according to Embodiment 1 of the present invention and the amount of desorbed source gas released from the shift catalyst 10a.
  • a predetermined amount of LPG is supplied directly to the burner unit 12 from the raw material gas supply unit 6 using the fuel processor 3 in which the shift converter 10 is filled only with the shift unit 10 experimentally prepared.
  • LPG which is a desorbed source gas, will be described as desorbed LPG as appropriate.
  • the horizontal axis of FIG. 3 indicates the elapsed time from the start of heating of the shift catalyst 10a
  • the first axis of the vertical axis indicates the flow rate of LPG
  • the second axis of the vertical axis indicates the temperature of the shift catalyst 10a.
  • the broken line in FIG. 3 indicates the amount of desorbed LPG that has been desorbed from the shift catalyst 10a
  • the solid line indicates the temperature of the shift catalyst 10a.
  • the amount of LPG, which is the source gas supplied from the source gas supply device 6 is indicated by a dashed line in order to compare with the amount of the desorbed LPG which has been desorbed from the shift catalyst 10a.
  • the temperature of the shift catalyst 10a gradually rises at a substantially constant rate from about 25 ° C., which is about the outside air temperature. Then, with the temperature rise of the shift catalyst 10a, the release of the released LPG from the shift catalyst 10a starts, and the amount of the released LPG continues to increase to about 60 ° C. Thereafter, while the amount of the desorbed LPG gradually decreases until the temperature of the shift catalyst 10a rises to about 180 ° C., it continues to be discharged.
  • the control unit 5 stores the correlation between the temperature of the shift catalyst 10a and the amount of desorbed LPG released from the shift catalyst 10a as a formula. Then, the amount of desorption LPG to be eliminated is estimated based on the temperature of the conversion catalyst 10a detected by the conversion temperature sensor 10b.
  • control unit 5 controls the amount of combustion air according to the amount of desorption LPG and the amount of LPG which is the source gas supplied to the burner unit.
  • the amount of LPG adsorbed to the shift catalyst 10a differs depending on the amount of the shift catalyst 10a to be charged and the shape and type of the shift catalyst 10a. Further, even if other hydrocarbon-based source gases such as city gas are used, the amount of adsorption adsorbed on the shift catalyst 10a is different. Further, since the shift temperature sensor 10b measures the temperature of a part of the shift catalyst 10a, the temperature and the amount of the desorbed source gas are different depending on the position of the shift temperature sensor 10b. Therefore, it is important to store in advance the relationship between the temperature of the shift catalyst 10a and the amount of desorbed source gas released from the shift catalyst 10a in the control unit 5 correspondingly.
  • the control unit 5 stores the relationship between the temperature of the reforming catalyst 9a and the temperature of the selective oxidation catalyst 11a and the amount of desorption LPG, thereby the reforming catalyst 9a and the selective oxidation catalyst 11a.
  • the amount of desorbed LPG desorbed from can be estimated.
  • the reforming catalyst 9a and the selective oxidation catalyst 11a used in the first embodiment have almost no adsorption of LPG, and with respect to the amount of LPG supplied from the raw material gas supply device 6, desorbing due to temperature rise is eliminated.
  • the amount of release LPG was sufficiently small. Therefore, the amount of the desorbed source gas from the shift catalyst 10a is controlled as a main parameter.
  • the raw material gas supply device 6 supplies LPG, which is a raw material gas mixed with the steam supplied from the steam generation device 4, to the reforming unit 9 in which the temperature of the reforming catalyst 9 a is maintained at about 700 ° C. Then, a reformed gas containing hydrogen, carbon monoxide, and steam is generated by the steam reforming reaction via the reforming catalyst 9 a of the reforming unit 9.
  • LPG is a raw material gas mixed with the steam supplied from the steam generation device 4
  • the reformed gas from the reforming unit 9 is supplied into the packed bed of the shift catalyst 10a of the shift unit 10, and flows upward from the lower side in the packed bed.
  • the shift catalyst 10a maintained at about 200 to 300 ° C.
  • a shift reaction occurs to generate carbon dioxide and hydrogen from carbon monoxide and steam contained in the reformed gas.
  • the concentration of carbon monoxide in the reformed gas is reduced to about 0.5% or less.
  • the reformed gas from the conversion unit 10 is separately supplied to the packed bed of the selective oxidation catalyst 11a of the selective oxidation unit 11 together with a small amount of air supplied through the selective oxidation air supply path 11b, and the packed bed It distributes from the bottom to the top.
  • carbon monoxide in the reformed gas is oxidized by the action of the selective oxidation catalyst 11a maintained at about 100 to 200.degree. Thereby, the concentration of carbon monoxide in the reformed gas is further reduced to about 10 ppm or less.
  • the reformed gas leaving the selective oxidation unit 11 passes through the raw material gas path 15 in which the fuel cell inlet valve 17 and the fuel cell outlet valve 18 are opened with the fuel cell bypass valve 16 closed, and the fuel cell 2 is supplied to the side of the anode electrode 2b. Then, a part of hydrogen in the reformed gas is consumed by power generation and the off gas discharged and the air supplied by the combustion air fan 7 are supplied to the burner unit 12 and burned in the burner unit 12. At this time, the reforming catalyst 9a is heated and maintained at about 700 ° C. by the heat of combustion of the off gas. Then, the combustion exhaust gas flows through the internal flow paths of the shift conversion unit 10 and the selective oxidation unit 11 to maintain the shift catalyst 10a at about 200 to 300 ° C. and the selective oxidation catalyst 11a at 150 to 200 ° C.
  • the electric power generated by the fuel cell 2 is consumed by an external load not shown.
  • the supply of air to the fuel cell 2 by the cathode air blower 8 and the supply of the source gas by the source gas supply device 6 are stopped.
  • the fuel cell bypass valve 16, the fuel cell inlet valve 17, and the fuel cell outlet valve 18 are closed.
  • the steam generator 4 is also stopped at the same time, and the supply of steam to the source gas supply path 14 via the steam path 4a is also stopped.
  • the fuel cell bypass valve 16 is opened, and the raw material gas supply device 6 reforms the LPG which is the raw material gas
  • the reformed gas containing steam is purged into the packed bed of each catalyst by sequentially supplying to the unit 9, the conversion unit 10 and the selective oxidation unit 11.
  • the temperatures of the shift catalyst 10a and the selective oxidation catalyst 11a are 100 ° C. or higher, the water vapor in the reformed gas does not condense on the surface of each catalyst.
  • LPG is supplied for a predetermined time during which the reformed gas containing water vapor can be sufficiently purged by LPG from the packed bed of each catalyst, and then the fuel cell bypass valve 16 is closed to stop the source gas supply device 6.
  • the pressure in the fuel processor 3 decreases due to the volume contraction of the LPG heated in the fuel processor 3.
  • the pressure in the fuel processor 3 is maintained at a positive pressure by supplying the LPG by the raw material gas supply device 6 every predetermined time.
  • an operation of supplying LPG into the fuel processor 3 in order to maintain a positive pressure will be described as a pressing operation.
  • LPG is sufficiently adsorbed to the shift catalyst 10a after the temperature decrease.
  • town gas and LPG are actually mixed gas of hydrocarbon gas components such as methane and propane, the ease of adsorption to the catalyst differs depending on each hydrocarbon gas.
  • a hydrocarbon gas component having a large molecular weight tends to be more easily adsorbed than a hydrocarbon gas component having a small molecular weight.
  • LPG used in the present embodiment has about 98% of propane as its main component, and therefore, there is no problem even if it is handled as a single gas of substantially propane. Therefore, the source gas component adsorbed to the shift catalyst 10a is also described as the source gas.
  • FIG. 4 is a flow chart showing a flow of control of main parts during startup operation of the fuel cell system according to Embodiment 1 of the present invention.
  • Step S1 the fuel cell bypass valve 16 is opened, and the raw material gas supply device 6 supplies LPG, which is a predetermined amount of raw material gas, to the reforming unit 9.
  • LPG flows sequentially to the conversion unit 10 and the selective oxidation unit 11 and is supplied to the burner unit 12 via the fuel cell bypass passage 15 b of the raw material gas passage 15.
  • the combustion air fan 7 blows air to the burner unit 12 at a flow rate corresponding to the flow rate of the LPG supplied by the raw material gas supply device 6 (step S1), and is ignited by the ignition device (step S2).
  • the reforming catalyst 9a of the reforming unit 9 is heated by the combustion heat, and the temperature (ThK) of the reforming catalyst 9a rises.
  • the combustion exhaust gas sequentially passes through the combustion exhaust gas path 13 inside the shift conversion unit 10 and the selective oxidation unit 11, whereby the shift catalyst 10a and the selective oxidation catalyst 11a are heated.
  • the temperature (ThH) of the shift catalyst 10a and the temperature (ThS) of the selective oxidation catalyst 11a rise.
  • the temperature (ThH) of the shift catalyst 10a is detected by the shift temperature sensor 10b and compared (step S3).
  • the temperature (ThH) of the shift catalyst 10a is lower than the predetermined temperature (Th1) (No in step S3), of the LPGs adsorbed to the shift catalyst 10a, the released LPG is desorbed.
  • the amount is estimated based on the information stored in the control unit 5 (step S4).
  • the amount of combustion air supplied to the burner unit 12 by the combustion air fan 7 is the sum of the amount of LPG supplied by the raw material gas supply device 6 and the amount (estimated value) of desorbed LPG that is desorbed.
  • the flow rate is adjusted to match (step S5).
  • the amount of combustion air matching the flow rate of LPG shown in step S1 and step S5 is necessary for completely burning LPG supplied to the burner unit 12 into carbon dioxide and water (steam). It is an amount of a predetermined multiple of the amount of air including the amount of oxygen. Therefore, in the following, the ratio between the amount of air and the amount of LPG will be described as an air-fuel ratio. That is, for example, an air-fuel ratio of 1.0 is a ratio at which the amount of oxygen in the supplied air and LPG are ideally combusted to become carbon dioxide and water without excess or deficiency. This indicates that half of the amount of oxygen in the supplied air is a ratio remaining in the flue gas without being used for combustion.
  • the air-fuel ratio in step S1 and step S5 is set to 2.5 to 3.0. If the air-fuel ratio is too large or too small, on the other hand, the ignitability may deteriorate, or incomplete combustion will occur even if the gas is ignited, carbon monoxide will be generated, and it will be released outside the fuel cell system as combustion exhaust gas. , Will be misfired.
  • step S5 the adjustment of the amount of combustion air based on the temperature detected by the shift temperature sensor 10b (step S5) is performed when the temperature (ThH) of the shift catalyst 10a is equal to or higher than a predetermined temperature (Th1) (Yes in step S3). Until the temperature (ThK) of the reforming catalyst 9a is 200 ° C. or higher, the temperature (ThH) of the shift catalyst 10a is 180 ° C. or higher, and the temperature (ThS) of the selective oxidation catalyst 11a reaches 150 ° C. (Step S6 Yes) Continue.
  • the temperature (ThK) of the reforming catalyst 9a is 200 ° C. or more, the temperature (ThH) of the conversion catalyst 10a is 180 ° C. or more, and the temperature (ThS) of the selective oxidation catalyst 11a reaches 150 ° C. Yes)
  • the supply of water vapor from the water vapor generator 4 to the source gas supply passage 14 via the water vapor passage 4a is started.
  • a mixed gas of LPG and steam is supplied into the packed bed of the reforming catalyst 9a of the reforming unit 9, and reforming of LPG to hydrogen is started (step S7).
  • the amount of combustion air is adjusted so that the air-fuel ratio becomes 1.5 to 2.0.
  • the steam may be condensed to inhibit the flow of gas. Therefore, the condition that the temperature (ThK) of the reforming catalyst 9a which is Yes in step S6 is 200 ° C. or more, the temperature (ThH) of the shift catalyst 10a is 180 ° C. or more, and the temperature (ThS) of the selective oxidation catalyst 11a is 150 ° C. or more Is the temperature of the temperature sensor for causing the overall temperature of each catalyst having a temperature distribution to be 100 ° C. or higher.
  • Step 8 whether the temperature of each catalyst is a predetermined temperature, that is, whether the temperature of the reforming catalyst 9a is about 600 to 700 ° C, the temperature of the shift catalyst 10a is about 200 to 300 ° C, and the temperature of the selective oxidation catalyst 11a is about 150 to 200 ° C.
  • the temperature of each catalyst is lower than the temperature range (No in step S8), the reaction with each catalyst is insufficient, that is, the amount of hydrogen in the reformed gas is small, and the amount of carbon monoxide is large.
  • the reformed gas in the middle of the temperature rise is caused to flow through the fuel cell bypass passage 15b.
  • step S8 when the temperature of each catalyst rises to a predetermined temperature range (Yes in step S8), the fuel cell bypass valve 16 is closed after the components of the reformed gas are stabilized. At the same time, the fuel cell inlet valve 17 and the fuel cell outlet valve 18 are opened, the reformed gas is supplied to the anode electrode 2b side of the fuel cell 2, and the power generation is started. Further, when the temperature of each catalyst is out of the temperature range (No in step S8), the same control as in the prior art is performed, and the process waits until the temperature range is reached.
  • the desorption of the source gas due to the temperature rise of the shift catalyst 10a during the start-up operation is made to the temperature of the shift catalyst 10a detected by the shift temperature sensor 10b.
  • the air for combustion is supplied to the burner unit 12 for combustion so as to have a predetermined air-fuel ratio with respect to the total amount of the estimated value and the supplied raw material gas.
  • the desorption amount of desorption LPG from the shift catalyst 10a at the time of start-up operation of the fuel cell system 1 is detected by the shift temperature sensor 10b for detecting the temperature of the shift catalyst 10a.
  • the example estimated based on the value has been described, it is not limited thereto.
  • FIG. 5 is a characteristic diagram showing how the temperatures of the reforming catalyst 9a, the shift catalyst 10a, and the selective oxidation catalyst 11a rise during start-up operation of the fuel cell system 1 of the present embodiment.
  • ThH) and the temperature (ThS) of the selective oxidation catalyst 11a are determined. Therefore, at the time of start-up operation of the fuel cell system, first, an elapsed time (t1) from the start of heating is measured by a timer, and the temperature of the shift catalyst 10a at that time is estimated. Then, based on the temperature of the shift catalyst 10a, the amount of released LPG to be released from the shift catalyst 10a is estimated.
  • the amount of combustion air is adjusted and controlled via the control unit 5 based on this estimation.
  • a temperature sensor that detects the temperature of the reforming catalyst 9a, a temperature sensor that detects the temperature of the selective oxidation catalyst 11a, etc. It is possible to substitute by
  • the shift temperature sensor 10b for detecting the temperature (ThH) of the shift catalyst 10a is provided.
  • the temperature (ThK, temperature of the reforming catalyst 9a and the selective oxidation catalyst 11a) There is no description of means for detecting the temperature of ThS).
  • a reforming temperature sensor for detecting the temperature of the reforming catalyst 9a and a selective oxidation temperature sensor for detecting the temperature of the selective oxidation catalyst 11a may be provided separately, or the temperature of the shift catalyst 10a detected by the shift temperature sensor 10b.
  • the temperatures of the reforming catalyst 9a and the selective oxidation catalyst 11a may be detected.
  • FIG. 6 is a flow chart for explaining the control flow of the main part of another method of start-up operation in the fuel cell system 1 according to Embodiment 1 of the present invention.
  • the fuel cell bypass valve 16 is opened, and the raw material gas supply device 6 and the combustion air fan 7 are operated. Air is supplied (step S1). Then, the LPG and the combustion air supplied to the burner unit 12 are ignited by the igniter (step S2). As a result, the combustion of LPG in the burner unit 12 starts, and the temperature (ThH) of the shift catalyst 10a rises.
  • the temperature (ThH) of the shift catalyst 10a is compared with a predetermined temperature (Th1) (step S3).
  • the source gas supply device 6 is stopped (step S4).
  • the supply of the raw material gas LPG from the raw material gas supply device 6 to the burner unit 12 is stopped, but since the desorbed LPG desorbed from the shift catalyst 10 a is supplied to the burner unit 12, combustion occurs. Will continue.
  • the temperature (ThH) of the shift catalyst 10a is compared with a predetermined temperature (Th2) (step S5).
  • the control unit removes the amount of LPG adsorbed on the shift catalyst 10a. It guesses by 5 (step S6).
  • the amount of combustion air supplied to the burner unit 12 by the combustion air fan 7 is adjusted to a flow rate corresponding to the amount of LPG desorbed from the shift catalyst 10a (step S7).
  • the raw material gas supply device 6 is operated again to supply LPG from the raw material gas supply device 6 to the burner unit 12 (Step S8).
  • the amount of combustion air supplied to the burner unit by the combustion air fan 7 is adjusted to a flow rate corresponding to the total amount of the amount of LPG supplied by the source gas supply device 6 and the amount of desorbed LPG. (Step S9).
  • step S9 the adjustment of the amount of combustion air based on the temperature detected by the shift temperature sensor 10b (step S9) is that the temperature (ThK) of the reforming catalyst 9a is 200 ° C. or higher and the temperature (ThH) of the shift catalyst 10a is It is continued until the temperature (ThS) of the selective oxidation catalyst 11a reaches 150 ° C. or more (Yes in step S10).
  • the temperature (ThK) of the reforming catalyst 9a is 200 ° C. or more, the temperature (ThH) of the conversion catalyst 10a is 180 ° C. or more, and the temperature (ThS) of the selective oxidation catalyst 11a reaches 150 ° C. Yes)
  • the supply of water vapor from the water vapor generator 4 to the source gas supply passage 14 via the water vapor passage 4a is started.
  • a mixed gas of LPG and steam is supplied into the packed bed of the reforming catalyst 9a of the reforming unit 9, and reforming of LPG to hydrogen is started (step S11).
  • the amount of combustion air is adjusted so that the air-fuel ratio becomes 1.5 to 2.0.
  • step S12 whether the temperature of each catalyst is a predetermined temperature, that is, whether the temperature of the reforming catalyst 9a is about 600 to 700 ° C, the temperature of the shift catalyst 10a is about 200 to 300 ° C, and the temperature of the selective oxidation catalyst 11a is about 150 to 200 ° C. Is determined (step S12). At this time, when the temperature of each catalyst is lower than the temperature range (No in step S12), the reaction with each catalyst is insufficient, that is, the amount of hydrogen in the reformed gas is small, and the amount of carbon monoxide is large. The reformed gas in the middle of the temperature rise is caused to flow through the fuel cell bypass passage 15b.
  • step S12 when the temperature of each catalyst rises to a predetermined temperature range (Yes in step S12), the fuel cell bypass valve 16 is closed after the components of the reformed gas are stabilized. At the same time, the fuel cell inlet valve 17 and the fuel cell outlet valve 18 are opened, the reformed gas is supplied to the anode electrode 2b side of the fuel cell 2, and the power generation is started.
  • the temperature rise of each catalyst was shown in FIG. 5 until step S8 in FIG. It can be slower than the temperature rise of each catalyst. This can suppress the occurrence of temperature distribution (variation) in the packed bed of each catalyst. In addition, it is possible to suppress deterioration of each catalyst and each cylinder constituting the fuel processor 3 due to a rapid temperature change.
  • the supply of the LPG by the raw material gas supply device is stopped after the temperature of the shift catalyst 10a reaches the predetermined temperature Th1, but the invention is not limited thereto.
  • the supply of the LPG by the raw material gas supply device 6 is stopped after a predetermined time has elapsed since the start of heating the shift catalyst 10a. You may
  • a configuration in which the raw material gas to be burned by the burner unit 12 is supplied to the burner unit 12 via the fuel processor 3 during start-up operation of the fuel cell system 1 is described as an example.
  • a path (not shown) for supplying the raw material gas directly from the raw material gas supply device to the burner unit 12 is provided, and the raw material gas is directly supplied to the burner unit 12 and burned when the fuel cell system 1 is started. It is also good.
  • the source gas path from the fuel processor 3 it is necessary to connect the source gas path from the fuel processor 3 to the burner unit 12.
  • the same effect can be obtained by estimating the amount of desorbed source gas desorbed from each catalyst and adjusting the amount of combustion air.
  • the fuel cell system 1 in which the amount of combustion air is adjusted only for the amount of the desorbed source gas desorbed from the shift conversion catalyst 10a is described as an example.
  • the reason for this is based on the experimental result that the amount of adsorption of the raw material gas LPG to the reforming catalyst 9a and the selective oxidation catalyst 11a used in the first embodiment is hardly present, and the influence on the air fuel ratio is sufficiently small. It is.
  • the source gas is adsorbed to the reforming catalyst 9a other than the shift catalyst 10a and the selective oxidation catalyst 11a. Then, the influence of the amount of desorbed raw material gas desorbed with the temperature rise on the air-fuel ratio may be increased.
  • the desorption amount of the desorption source gas due to the temperature rise of each catalyst is experimentally obtained for each of the reforming unit 9, the transformation unit 10 and the selective oxidation unit 11 to start the fuel cell system 1 During operation, the amount of desorbed source gas desorbed from each catalyst is estimated from the temperature of each catalyst.
  • the amount of combustion air is set so that the air-fuel ratio becomes a predetermined ratio with respect to the total amount of the amount of desorption source gas desorbed from each catalyst and the source gas supplied from the source gas supply device. You may adjust and control. As a result, the occurrence of incomplete combustion can be further suppressed, and a highly reliable fuel cell system that can be reliably started and operated can be realized.
  • FIG. 7 is a schematic view showing a configuration of a fuel cell system 1 according to Embodiment 2 of the present invention.
  • the same reference numerals in FIG. 7 denote the same components as in FIG. 1, and a description thereof will be omitted.
  • the transformation heater 30 of the fuel cell system 1 shown in Embodiment 1 is provided with a transformation heater 31, and the selective oxidation heater 32 is provided in the selective oxidation unit 32. It differs from the fuel cell system 1 of the first embodiment in that it is provided.
  • the metamorphic heater 31 is installed outside the metamorphic part 30 not in contact with the metamorphic catalyst 10 a, and the selective oxidation catalyst 11 a of the selective oxidation part 32
  • the selective oxidation heater 33 is provided on the outside which does not contact.
  • the metamorphic heater 31 and the selective oxidation heater 33 are, for example, electric heaters or the like, which generate heat when energized and heat the metamorphic unit 30 and the selective oxidation unit 32.
  • FIG. 8 is a flow chart showing the flow of control of the main part during start-up operation of the fuel cell system 1 according to Embodiment 2 of the present invention. The detailed description of the same parts as the first embodiment of the present invention may be omitted.
  • the raw material gas supply device 6 supplies LPG as the raw material gas and the combustion air to the burner unit 12 by the combustion air fan 7 (step S1) .
  • the supplied LPG and the combustion air are ignited and burned by an ignition device (not shown) (step S2).
  • the combustion exhaust gas flows sequentially through the combustion exhaust gas passage 13 provided inside the selective oxidation unit 11 not in direct contact with the shift converter 30 and the selective oxidation catalyst 11 a in direct contact with the shift catalyst 10a.
  • the catalyst 10a and the selective oxidation catalyst 11a begin to heat.
  • the shift heater 31 and the selective oxidation heater 33 are energized to heat the shift catalyst 10a and the selective oxidation catalyst 11a also from the outside (step S2a).
  • the heating by the transformation heater 31 and the selective oxidation heater 33 is continued until the temperature (ThH) of the transformation catalyst 10a detected by the transformation temperature sensor 10b reaches a predetermined temperature (Tha) (Yes in step S3a).
  • the energization of the shift heater 31 and the selective oxidation heater 33 is stopped, and only heating by the combustion exhaust gas is performed.
  • the predetermined temperature (Tha) will be described later.
  • the control unit 5 compares the temperature (ThH) of the shift catalyst 10a with a predetermined temperature (Th1) (step S3). Then, until the temperature (ThH) of the shift catalyst 10a detected by the shift temperature sensor 10b exceeds the predetermined temperature (Th1) (No in step S3), the shift catalyst 10a is operated based on the temperature (ThH) of the shift catalyst 10a. The amount of desorbed LPG is estimated (step S4). Further, it is added up with the amount of the raw material gas LPG supplied by the raw material gas supply device 6, and is burned by the burner unit 12 together with a predetermined amount of combustion air (step S5).
  • the above operation is the same as that of the first embodiment.
  • the temperature distribution of the shift catalyst 10a at the temperature detected by the shift temperature sensor 10b. May differ from the case of the first embodiment. Therefore, the temperature (ThH) detected by the transformation temperature sensor 10b and the desorption amount of LPG from the transformation catalyst 10a may differ depending on the position of the transformation temperature sensor 10b depending on whether the transformation heater 31 is present or not.
  • the predetermined temperature (Tha) for continuing heating by the shift heater 31 and the selective oxidation heater 33 is, first, mixing steam with feed gas at 100 ° C. or higher of the shift catalyst 10 a and the selective oxidation catalyst 11 a And a temperature at which the water vapor is mixed with the LPG and supplied to the fuel processor 3.
  • the shift temperature sensor 10 b detects approximately 180 ° C.
  • control is performed so as to turn off the shift heater 31 and the selective oxidation heater.
  • the temperature of the selective oxidation catalyst was also about 150.degree.
  • the desorption of the source gas due to the temperature rise of the shift catalyst 10a during the start-up operation is made to the temperature of the shift catalyst 10a detected by the shift temperature sensor 10b.
  • the air for combustion is supplied to the burner unit 12 for combustion so as to have a predetermined air-fuel ratio with respect to the total amount of the estimated value and the supplied raw material gas.
  • the occurrence of incomplete combustion can be suppressed to realize stable combustion, and the start-up operation of the fuel cell system 1 can be reliably performed.
  • the rise time of the start-up operation of the fuel cell system 1 can be shortened.
  • the fuel cell system 1 has been described as being started up using the conversion heater 31 and the selective oxidation heater 33.
  • the selective oxidation heater 33 may not be provided, and only the metamorphic heater may be used.
  • the selective oxidation catalyst 11a can be heated in a short time as compared with the case where the shift heater 31 is not provided because it is supplied into the packed bed 11a. As a result, it is effective for construction of the fuel cell system 1 that is required to have a low cost and a short start-up start time.
  • the electric heater is described as an example of the transformation heater 31 and the selective oxidation heater 33, but the invention is not limited thereto.
  • a heating burner unit having the same configuration as the burner unit 12 may be provided.
  • the burner unit may be used as a heating burner unit. This can further simplify the configuration.
  • the heating burner unit may be configured to further heat the reforming unit 9.
  • FIG. 9 is a flow chart for explaining the control flow of the main part of another start-up operation method in the fuel cell system 1 of the second embodiment of the present invention.
  • the fuel cell bypass valve 16 is opened, and the raw material gas is supplied to the burner unit 12 by driving the raw material gas supply device 6 and the combustion air fan 7. LPG and combustion air are supplied (step S1). Then, ignition is performed using an ignition device (not shown) to start combustion of LPG (step S2).
  • step S3 After confirming the temperature rise of the shift catalyst 10a by the shift temperature sensor 10b, energization of the shift heater 31 and the selective oxidation heater 33 is started, and heating of each catalyst by the heaters is started (step S3). At this time, the supply of the source gas by the source gas supply device 6 is stopped, and only the desorption source gas desorbed from the shift catalyst 10a is burned as the shift catalyst 10a is heated (Step S4).
  • the temperature (ThH) of the shift catalyst 10a is compared with a predetermined temperature (Th1) (step S5). Then, until the temperature (ThH) of the shift catalyst 10a exceeds the predetermined temperature (Th1) (No in step S5), first, desorption from the shift catalyst 10a is performed based on the temperature of the shift catalyst 10a detected by the shift temperature sensor 10b. The amount of the desorbed source gas is estimated (step S6). Thereafter, the amount of air blown by the combustion air fan 7 is adjusted (step S7). Then, the fuel cell system is activated according to the flow of control in step S10 and subsequent steps as in the other embodiments.
  • step S5 When the temperature (ThH) of the shift catalyst 10a exceeds the predetermined temperature (Th1) (Yes in step S5), the source gas supply device 6 is operated with the ignition device (not shown) operated after the predetermined time has elapsed. The supply of the source gas LPG is resumed (step S8).
  • the amount of combustion air supplied to the burner unit 12 by the combustion air fan 7 is a flow rate corresponding to the total amount of the amount of LPG supplied by the raw material gas supply device 6 and the amount of desorbed LPG. Adjust (step S9).
  • the fuel cell system 1 performs the start-up operation according to the flow of control in step S10 and subsequent steps as in the other embodiments.
  • the combustion may be continued until a predetermined time until Th1) is reached.
  • the flow rate of the desorbed LPG desorbed from the shift catalyst 10a when the shift catalyst 10a sufficiently adsorbs the LPG corresponds to the raw material gas supply device. 6 refers to the temperature of the shift catalyst 10a which becomes sufficiently small to such an extent that the air fuel ratio is not significantly affected with respect to the flow rate of the raw material gas LPG supplied by 6 and its elapsed time.
  • the combustion with the raw material gas supplied from the raw material gas supply device is carried out at the same time as the raw material gas supplied from the raw material gas supply device by burning preferentially the desorbed raw material gas desorbed from the raw material gas Even if the flow rate of the source gas supplied by the source gas supply device is increased, it is possible to moderate the temperature rise of the reforming catalyst 9a. As a result, variation in temperature distribution in the packed bed of the reforming catalyst 9a, which occurs when the temperature rise of the reforming catalyst 9a is rapid, damage to the reforming catalyst 9a due to stress due to rapid temperature change, etc. Can be prevented in advance. As a result, it is possible to realize the stable start-up operation and the fuel cell system 1 that operates reliably over a long period of time.
  • the flow rate of the source gas supplied from the source gas supply device Needs to be reduced sufficiently.
  • the amount of the raw material of reformed gas necessary for power generation is maintained while maintaining the temperature of the reforming section 9 performing steam reforming which is an endothermic reaction at about 700.degree. It is necessary to supply the source gas. Therefore, a raw material gas supply device capable of supplying the raw material gas by controlling the flow rate over a wide range is required, leading to an increase in size and complexity of the device.
  • the temperature rise of the shift catalyst 10a can be controlled by the on / off control of the shift heater 31 and the adjustment of the heater output. Furthermore, the flow rate of the desorbed source gas desorbed from the shift catalyst 10a can also be adjusted. As a result, it is possible to realize a fuel cell system capable of controlling the temperature rise speed of the reforming catalyst 9a with a relatively simple configuration.
  • LPG which is the raw material gas
  • heater heating is started after ignition by the ignition device to supply LPG from the raw material gas supply device.
  • the heater heating of the shift catalyst 10a may be started first to ignite the desorbed desorbed LPG, and the same effect and function can be obtained.
  • the electric heater is described as an example of the transformation heater 31 and the selective oxidation heater 33, but the invention is not limited thereto.
  • the same configuration as the burner unit 12 may be provided, and a heating burner unit used to heat the catalyst during start-up operation may be provided.
  • FIG. 10 is a configuration diagram for explaining another example of the fuel cell system according to Embodiment 2 of the present invention.
  • the fuel cell system 1 of the present embodiment further includes a burner unit 12, a heating burner unit 34, a pre-burner switching valve 35, and a combustion air path switching valve 36.
  • the pre-burner switching valve 35 switches and supplies the source gas from the source gas path 15 to the burner portion 12 or the heating burner portion 34 based on the signal of the control unit 5.
  • the combustion air path switching valve 36 switches the combustion air to the burner unit 12 or the heating burner unit 34 based on the signal of the control unit 5 and supplies it. Then, like the burner unit 12, the heating burner unit 34 heats and heats the reforming catalyst 9a, the shift catalyst 10a, and the selective oxidation catalyst 11a with the combustion heat and the combustion exhaust gas.
  • the heating burner unit 34 can be made smaller than the burner unit 12 and can burn even a small amount of raw material gas, and can improve the controllability of the temperature rise of each catalyst. Therefore, the heating amount of the catalyst can be adjusted with relatively high accuracy by using the heating burner unit 34 at the start-up operation of the fuel cell system.
  • the temperature rise speed of the catalyst is controlled with relatively high accuracy, and the amount of the desorbed source gas is accurately adjusted. it can.
  • it is possible to realize a fuel cell system capable of stable start-up operation by keeping the air-fuel ratio in the burner unit 12 within a predetermined range.
  • FIG. 11 is a schematic view showing a configuration of a fuel cell system 1 according to Embodiment 3 of the present invention.
  • the same components as those of the fuel cell system 1 according to the first and second embodiments will be assigned the same reference numerals and descriptions thereof will be omitted.
  • a flowmeter 40 for circulating the raw material gas passage 15 is provided in the raw material gas passage 15 of the fuel cell system 1 shown in the first embodiment. It differs from the fuel cell system of the first embodiment in the point.
  • the flow rate meter 40 is the sum of the flow rate of the raw material gas supplied from the raw material gas supply device 6 and the flow rate of the desorbed raw material gas desorbed from the catalyst of the fuel processor 3 during start-up operation of the fuel cell system 1 It measures.
  • the combustion gas supplied to the burner unit 12 is separated from the raw material gas supplied from the raw material gas supply device 6 and the catalyst of the fuel processor 3. It shows the thing with coming out desorption source gas.
  • the flow meter 40 is wired so as to input the flow rate of the combustion gas measured by the flow meter 40 to the control unit 5 as a signal.
  • FIG. 12 is a flow chart showing the flow of control of the main part during start-up operation of the fuel cell system 1 of Embodiment 3. The detailed description of the same parts as those of the other embodiments of the present invention may be omitted.
  • LPG which is the raw material gas in the raw material gas supply device 6, combustion air by the combustion air fan 7 and predetermined flow rates in the burner unit 12.
  • Supply step S1
  • LPG which is a source gas
  • LPG is first supplied to the reforming unit 9 via the source gas supply path 14, and is sequentially distributed to the metamorphic unit 10 and the selective oxidation portion 11, and fuel cell bypass of the source gas path 15. It is supplied to the burner unit 12 via the path 15b.
  • only LPG which is the source gas supplied from the source gas supply device 6, is supplied to the burner unit 12 as the combustion gas.
  • the supplied LPG and the combustion air are ignited by an ignition device (not shown) to start the combustion (step S2).
  • the combustion of LPG in the burner unit 12 starts, the heat of combustion starts heating the reforming catalyst 9a of the reforming unit 9, and the temperature (ThK) of the reforming catalyst 9a starts to rise.
  • the combustion exhaust gas passes through the combustion exhaust gas passage 13 formed inside the shift conversion unit 10 and the selective oxidation unit 11, whereby the shift catalyst 10a and the selective oxidation catalyst 11a begin to be heated.
  • the temperature (ThH) of the shift catalyst 10a and the temperature (ThS) of the selective oxidation catalyst 11a begin to rise.
  • LPG adsorbed on the shift catalyst 10a starts to be desorbed, and is supplied to the burner unit 12 as desorbed LPG. Therefore, LPG, which is the source gas supplied from the source gas supply device 6 as the combustion gas, and the desorbed LPG are supplied to the burner unit 12.
  • the flow meter 40 starts detecting the flow rate of the combustion gas, and the control unit 5 starts adjusting the flow rate of the combustion air based on the flow rate of the combustion gas detected by the flow meter 40 (step S3) .
  • the temperature (ThK) of the reforming catalyst 9a, the temperature (ThH) of the shift catalyst 10a, and the temperature (ThS) of the selective oxidation catalyst 11a are respectively compared with predetermined temperatures (step S4). If any of the temperature (ThK) of the reforming catalyst 9a, the temperature (ThH) of the shift catalyst 10a, and the temperature (ThS) of the selective oxidation catalyst 11a is lower than a predetermined temperature (No in step S4), the flowmeter 40 is selected.
  • the temperature (ThK) of the reforming catalyst 9a is 200 ° C., and the transformation is performed at a predetermined temperature.
  • the temperature (ThH) of the catalyst 10 a was 180 ° C.
  • the temperature (ThS) of the selective oxidation catalyst 11 a was 150 ° C.
  • step S4 When all of the reforming catalyst 9a temperature (ThK), the temperature of the shift catalyst 10a (ThH) and the temperature of the selective oxidation catalyst 11a (ThS) become equal to or higher than a predetermined temperature (Yes in step S4), the steam path 4a from the steam generator 4 The supply of steam to the raw material gas supply path 14 is started via the above, and the flow control of the combustion air based on the measurement value of the flow meter 40 is ended. Then, a mixed gas of LPG and steam is supplied into the packed bed of the reforming catalyst 9a of the reforming unit 9, and reforming of LPG to hydrogen is started (step S5).
  • the reason that the flow control of the combustion air based on the measurement value of the flow meter 40 is ended with the start of the supply of the steam is that the composition of the combustion gas flowing through the flow meter 40 contains This is because the reformed gas contains steam in addition to the quality gas, so that the flow rate of the combustion gas can not be accurately measured by the flowmeter 40.
  • the flow rate of the combustion air is LPG which is the raw material gas supplied by the raw material gas supply device 6. Is adjusted based on the flow rate of
  • Step 6 it is determined whether the temperature of each catalyst is within a predetermined temperature range, that is, the reforming catalyst is about 600-700 ° C., the conversion catalyst is about 200-300 ° C., and the selective oxidation catalyst is about 150-200 ° C. (Step 6). At this time, when the temperature of each catalyst is lower than the temperature range (No in step S6), the reaction with each catalyst is insufficient, that is, the amount of hydrogen in the reformed gas is small, and the amount of carbon monoxide is large. The reformed gas in the middle of the temperature rise is caused to flow through the fuel cell bypass passage 15b.
  • step S6 When the temperature of each catalyst rises to a predetermined temperature range (Yes in step S6), the fuel cell bypass valve 16 is closed after the components of the reformed gas are stabilized. At the same time, the fuel cell inlet valve 17 and the fuel cell outlet valve 18 are opened, the reformed gas is supplied to the anode electrode 2b side of the fuel cell 2, and the power generation is started. In addition, when the temperature of each catalyst is out of the temperature range (No in step S6), the same control as in the prior art is performed, and the process waits until the temperature range is reached.
  • the raw material to be supplied from the raw material gas supply device is the flow rate of the desorbed raw material gas desorbed due to the temperature rise of the shift catalyst 10a at the time of start-up operation. Since it is possible to measure the flow rate of the gas together with the flow rate of the gas and adjust the flow rate of the combustion air based on the measurement value of the flow rate 40, it is possible to stabilize the combustion in the burner unit 12 is there. As a result, the occurrence of incomplete combustion can be suppressed to realize stable combustion, and the start-up operation of the fuel cell system 1 can be reliably performed.
  • the flow meter 40 is provided in the source gas path, but may be provided in the fuel cell bypass path or the off gas path.
  • the raw material gas supplied from the raw material gas supply device is supplied to the burner unit 12 through the fuel processor 3 at the time of start-up operation of the fuel cell system 1.
  • the source gas supplied from the source gas supply device is supplied to the burner unit 12 through the fuel processor 3 at the time of start-up operation of the fuel cell system 1.
  • the source gas supplied from the source gas supply device is supplied to the burner unit 12 through the fuel processor 3 at the time of start-up operation of the fuel cell system 1.
  • the temperature of each catalyst of the fuel processor 3 is sufficiently reduced in carbon monoxide concentration at the initial start of the fuel cell system
  • the fuel cell system may be configured to supply the raw material gas supplied from the raw material gas supply device directly to the burner unit via the branch path until the predetermined temperature suitable for generating the reformed gas ofIn this case, the flow meter measures the flow rate of the desorbed raw material gas desorbed from each catalyst of the fuel processor 3, and the control unit 5 measures the flow rate of the desorbed raw material gas measured by the flow meter 40 By controlling the combustion air
  • the flow rate of the raw material gas supplied from the raw material gas supply device using the flow meter 40 and the desorbed raw material desorbed from each catalyst of the fuel processor 3 Although the total amount of gas flow rates was measured, a pressure gauge may be used. That is, for example, a pressure gauge is connected to the source gas path, and the relationship between the gas flow rate flowing through the source gas path and the pressure is stored in the control unit 5 in advance.
  • the flow rate of the raw material gas supplied to the burner unit 12 based on the value measured by the meter that is, the flow rate of the raw material gas supplied from the raw material gas supply device and the desorbed raw material gas desorbed from each catalyst of the fuel processor 3
  • the same effect as in the third embodiment can be obtained by estimating the sum of the flow rate and the flow rate, and controlling the flow rate of combustion air supplied from the combustion air fan by the control unit based on the estimated value. it can.
  • the source gas is not limited to this as in the other embodiments, and other hydrocarbon-based gas such as city gas or kerosene may be used. It is also possible to use raw materials. In the case of using a liquid hydrocarbon-based material such as kerosene, it is preferable to evaporate it into a gas.
  • the type of the source gas changes, it is predicted that the amount of the source gas adsorbed to each catalyst of the fuel processor 3, the temperature of each catalyst, and the behavior of the desorption source gas flow rate differ.
  • the flow rate of the raw material gas including the desorbed raw material gas supplied to the burner unit 12 is measured, and the flow rate of the combustion air is adjusted based on the measured value. It is possible to stabilize the combustion at 12.
  • the flowmeter 40 needs to use the flowmeter 40 capable of measuring the flow rate of the source gas depending on the type of the source gas.
  • the timing at which the flow rate control of the combustion air based on the flow rate of the raw material gas detected by the flow meter 40 ends is the temperature of each catalyst of the fuel processor 3 Reaches the predetermined temperature and the same as the timing to supply steam, but this is the temperature at which the temperature of each catalyst rises and the desorbed raw material gas does not affect the combustion in the burner section 12 If it exceeds, it is not restricted to this.
  • FIG. 13 is a schematic view showing a configuration of a fuel cell system 1 according to Embodiment 4 of the present invention.
  • the same components as those of the fuel cell system 1 in the first to third embodiments described above are assigned the same reference numerals and descriptions thereof will be omitted.
  • the fuel cell system 1 of Embodiment 4 corresponds to the exhaust gas analysis means of the fuel cell system 1 of the fuel cell system 1 shown in Embodiment 1, and the oxygen concentration in the combustion exhaust gas is
  • the fuel cell system is different from the fuel cell system according to the first embodiment in that an oximeter 41 is provided to measure.
  • the oxygen concentration meter 41 measures the oxygen concentration in the combustion exhaust gas after burning the raw material gas, the off gas, the reformed gas, etc. together with the combustion air in the burner unit 12. It is electrically connected to be input as a signal.
  • FIG. 14 is a flow chart showing the flow of control of the main part during start-up operation of the fuel cell system 1 of the fourth embodiment. The detailed description of the same parts as those of the other embodiments of the present invention may be omitted.
  • LPG which is the raw material gas in the raw material gas supply device 6, combustion air in the combustion air fan 7, and predetermined flow rates in the burner unit 12.
  • Supply step S1
  • LPG which is a source gas
  • LPG is first supplied to the reforming unit 9 via the source gas supply path 14, and is sequentially distributed to the metamorphic unit 10 and the selective oxidation portion 11, and fuel cell bypass of the source gas path 15. It is supplied to the burner unit 12 via the path 15b.
  • only LPG which is the source gas supplied from the source gas supply device 6, is supplied to the burner unit 12 as the combustion gas.
  • the supplied LPG and the combustion air are ignited by an ignition device (not shown) to start the combustion (step S2).
  • the combustion of LPG in the burner unit 12 starts, the heat of combustion starts heating the reforming catalyst 9a of the reforming unit 9, and the temperature (ThK) of the reforming catalyst 9a starts to rise.
  • the combustion exhaust gas passes through the combustion exhaust gas passage 13 formed inside the shift conversion unit 10 and the selective oxidation unit 11, whereby the shift catalyst 10a and the selective oxidation catalyst 11a begin to be heated.
  • the temperature (ThH) of the shift catalyst 10a and the temperature (ThS) of the selective oxidation catalyst 11a begin to rise.
  • Step S3 measurement of the oxygen concentration in the combustion exhaust gas discharged from the burner unit 12 is started by the oximeter 41, and input to the control unit 5 is started.
  • the control unit 5 adjusts the flow rate of the fuel air by controlling the combustion fan based on the oxygen concentration measured by the oxygen concentration meter 41 so that the oxygen concentration measured by the oxygen concentration meter 41 becomes a predetermined oxygen concentration.
  • Step S3 Specifically, when the oxygen concentration in the combustion exhaust gas measured by the oximeter 41 is lower than a predetermined oxygen concentration, the flow rate of the combustion air supplied from the combustion air fan 7 is increased, and conversely, in the combustion exhaust gas If the oxygen concentration is higher than the predetermined oxygen concentration, the flow rate of the combustion air supplied from the combustion air fan 7 is reduced.
  • the source gas supplied from the source gas supply device 6 to the burner unit 12 and the removal from the catalyst Although the total amount with the source gas is supplied, the flow rate of the source gas supplied to the burner unit 12 is adjusted because the flow rate of the combustion air is adjusted based on the oxygen concentration in the combustion exhaust gas. The combustion air of the flow rate corresponding to is supplied.
  • the temperature (ThK) of the reforming catalyst 9a, the temperature (ThH) of the shift catalyst 10a, and the temperature (ThS) of the selective oxidation catalyst 11a are respectively compared with predetermined temperatures (step S4).
  • the oxygen concentration meter 41 Continue adjusting the flow rate of the combustion air based on the oxygen concentration in the combustion exhaust gas detected in
  • the temperature (ThK) of the reforming catalyst 9a is 200 ° C.
  • the conversion catalyst 10a has a predetermined temperature.
  • the selective oxidation catalyst 11a was 150.degree. C.
  • the temperature (ThH) of the selective oxidation catalyst 11a was 150.degree.
  • step S4 When all of the reforming catalyst 9a temperature (ThK), the temperature of the shift catalyst 10a (ThH) and the temperature of the selective oxidation catalyst 11a (ThS) become equal to or higher than a predetermined temperature (Yes in step S4), the steam path 4a from the steam generator 4 The supply of steam to the source gas supply path 14 is started via the above, and the flow rate control of the combustion air based on the measurement value of the oximeter 41 is ended. Then, a mixed gas of LPG and steam is supplied into the packed bed of the reforming catalyst 9a of the reforming unit 9, and reforming of LPG to hydrogen is started (step S5).
  • the temperature (ThH) of the shift catalyst 10a becomes equal to or higher than a predetermined temperature (180 ° C. in this case)
  • the desorbed raw material gas (desorbed LPG in this embodiment) from the catalyst almost disappears as shown in FIG. Since the combustion in the burner unit 12 is not affected, the flow rate of the combustion air is adjusted based on the flow rate of the raw material gas LPG supplied by the raw material gas supply device 6.
  • Step S6 it is determined whether the temperature of each catalyst is within a predetermined temperature range, that is, the reforming catalyst is about 600-700 ° C., the conversion catalyst is about 200-300 ° C., and the selective oxidation catalyst is about 150-200 ° C. (Step S6).
  • the temperature of each catalyst is lower than the temperature range (No in step S6), the reaction with each catalyst is insufficient, that is, the amount of hydrogen in the reformed gas is small, and the amount of carbon monoxide is large.
  • the reformed gas in the middle of the temperature rise is caused to flow through the fuel cell bypass passage 15b.
  • step S6 When the temperature of each catalyst rises to a predetermined temperature range (Yes in step S6), the fuel cell bypass valve 16 is closed after the components of the reformed gas are stabilized. At the same time, the fuel cell inlet valve 17 and the fuel cell outlet valve 18 are opened, the reformed gas is supplied to the anode electrode 2b side of the fuel cell 2, and the power generation is started. In addition, when the temperature of each catalyst is out of the temperature range (No in step S6), the same control as in the prior art is performed, and the process waits until the temperature range is reached.
  • the flow rate of the combustion air is adjusted based on the oxygen concentration in the combustion exhaust gas at the time of start-up operation. Even when the temperature of the catalyst rises and the raw material gas adsorbed to the catalyst is desorbed and supplied to the burner unit, it is possible to stabilize the combustion in the burner unit. As a result, the occurrence of incomplete combustion can be suppressed to realize stable combustion, and start-up operation of the fuel cell system can be reliably performed.
  • the flow rate of combustion air is adjusted so that the oxygen concentration in the combustion exhaust gas becomes a predetermined concentration using an oximeter that measures the oxygen concentration in the combustion exhaust gas.
  • this may use a carbon dioxide concentration meter that measures the carbon dioxide concentration in the flue gas.
  • the fuel cell system according to the present invention can perform stable start-up operation together with stable combustion of the burner unit, it can be used in the technical field of a fuel cell system using steam reforming of hydrocarbon gas such as city gas and LPG. It is useful.

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  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention porte sur un système de pile à combustible capable de réaliser une opération de démarrage stable et une combustion stable dans une unité de brûleur durant l'opération de démarrage du système de pile à combustible. Durant l'opération de démarrage du système de pile à combustible, la quantité d'air de combustion délivré à l'unité de brûleur (12) par une soufflante est ajustée selon la quantité agrégée de gaz source fourni à l'unité de brûleur (12) par une unité d'alimentation en gaz source (6) et la quantité estimée de gaz source parmi les composants de gaz source adsorbés dans le catalyseur d'un processeur de combustible (3) qui sont séparés en raison de l'élévation de température du catalyseur et fournis à l'unité de brûleur (12).
PCT/JP2010/002092 2009-03-27 2010-03-24 Système de pile à combustible WO2010109863A1 (fr)

Priority Applications (4)

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JP2011505872A JP5173019B2 (ja) 2009-03-27 2010-03-24 燃料電池システム
US13/057,657 US8507136B2 (en) 2009-03-27 2010-03-24 Fuel cell system
CN2010800024699A CN102138240A (zh) 2009-03-27 2010-03-24 燃料电池系统
EP10755665A EP2413411A4 (fr) 2009-03-27 2010-03-24 Système de pile à combustible

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JP2009-078441 2009-03-27
JP2009078441 2009-03-27

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WO2010109863A1 true WO2010109863A1 (fr) 2010-09-30

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EP (1) EP2413411A4 (fr)
JP (1) JP5173019B2 (fr)
KR (1) KR20110120354A (fr)
CN (1) CN102138240A (fr)
WO (1) WO2010109863A1 (fr)

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WO2015118860A1 (fr) * 2014-02-05 2015-08-13 パナソニックＩｐマネジメント株式会社 Dispositif de production d'hydrogène et procédé de fonctionnement pour le dispositif de production d'hydrogène
JP2017137209A (ja) * 2016-02-03 2017-08-10 パナソニックＩｐマネジメント株式会社 水素生成装置と、それを備えた燃料電池システム、および、それらの運転方法
JP2018174056A (ja) * 2017-03-31 2018-11-08 パナソニックＩｐマネジメント株式会社 燃料電池システム

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WO2010131447A1 (fr) * 2009-05-12 2010-11-18 パナソニック株式会社 Système de pile à combustible
WO2010131448A1 (fr) * 2009-05-12 2010-11-18 パナソニック株式会社 Système de pile à combustible
CN109346749B (zh) * 2018-09-28 2021-11-26 武汉长海高新技术有限公司 一种燃料电池电堆尾气检测模块

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WO2015118860A1 (fr) * 2014-02-05 2015-08-13 パナソニックＩｐマネジメント株式会社 Dispositif de production d'hydrogène et procédé de fonctionnement pour le dispositif de production d'hydrogène
JPWO2015118860A1 (ja) * 2014-02-05 2017-03-23 パナソニックＩｐマネジメント株式会社 水素生成装置および水素生成装置の運転方法
JP2017137209A (ja) * 2016-02-03 2017-08-10 パナソニックＩｐマネジメント株式会社 水素生成装置と、それを備えた燃料電池システム、および、それらの運転方法
JP2018174056A (ja) * 2017-03-31 2018-11-08 パナソニックＩｐマネジメント株式会社 燃料電池システム

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JP5173019B2 (ja) 2013-03-27
EP2413411A4 (fr) 2013-03-27
US20110143230A1 (en) 2011-06-16
KR20110120354A (ko) 2011-11-03
EP2413411A1 (fr) 2012-02-01
CN102138240A (zh) 2011-07-27
US8507136B2 (en) 2013-08-13
JPWO2010109863A1 (ja) 2012-09-27

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